JPH0427940B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to a soft vinyl chloride resin multilayer laminate and its production, which has extremely little elution of plasticizers and does not impair the original transparency, flexibility, etc. of the soft vinyl chloride resin. It is about the method. [Prior Art] Soft vinyl chloride resins with added plasticizers are widely used for various medical devices such as blood circuits, food packaging, etc. due to their excellent transparency, flexibility, and processability. However, it is known that when a soft vinyl chloride resin product containing a plasticizer etc. is brought into contact with an aqueous solvent such as water, blood, etc., the plasticizer etc. will be eluted. Various methods for preventing the elution of plasticizers have been studied in the past, for example,
There are plasma treatments as seen in publications such as
It is difficult to sufficiently treat the inner surface of a narrow tube, and there is also a concern that other performances such as antithrombotic properties may deteriorate due to plasma treatment. Additionally, multilayer laminates of soft vinyl chloride resins and polyurethane or EVA (ethylene-vinyl acetate copolymer) have been proposed, but at present they have not been able to sufficiently prevent plasticizer elution. Furthermore, when using a non-migratory plasticizer, such as a polyester plasticizer, there is a problem that a sufficient plasticizing effect cannot be obtained. [Purpose of the Invention] The present invention is based on various studies aimed at significantly reducing the elution of plasticizers, etc. from soft vinyl chloride resins, and obtaining molded products with excellent antithrombotic properties in the medical field. As a result, when an ethylene-vinyl alcohol copolymer with excellent oxygen gas barrier properties is combined with a soft vinyl chloride resin to form a multilayer laminate, almost no plasticizer can pass through, even when it comes into contact with an aqueous solvent or blood. I have learned that it is not allowed. This is the result of applying the knowledge that the present inventors previously disclosed in Japanese Patent Application No. 58-203699 etc. that addition polymerization type silicone compositions exhibit excellent adhesion to soft vinyl chloride resins. discovered that a soft vinyl chloride resin and an ethylene-vinyl alcohol copolymer could be bonded together using an addition-polymerized liquid silicone rubber, and conducted various studies to complete the present invention. The purpose is to significantly reduce or prevent the elution of plasticizers, etc., without impairing the transparency and flexibility of soft vinyl chloride resins, and to create products with excellent antithrombotic properties in the medical field. An object of the present invention is to provide a soft vinyl chloride resin multilayer laminate. [Structure of the Invention] That is, the present invention provides a flexible vinyl chloride resin multilayer laminate comprising at least three layers of a flexible vinyl chloride resin, an ethylene-vinyl alcohol copolymer, and an addition-polymerized silicone rubber. In particular, at least three layers constituting the laminate are soft vinyl chloride resin/addition silicone rubber/ethylene-vinyl alcohol copolymer, or soft vinyl chloride resin/addition silicone rubber/ethylene-vinyl alcohol. The present invention relates to a soft vinyl chloride resin multilayer laminate characterized in that a copolymer/addition polymer silicone rubber are laminated in this order, and a method for producing the same. In the present invention, the soft vinyl chloride resin refers to vinyl chloride homopolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate terpolymer, vinyl chloride -The main component is a copolymer mainly composed of vinyl chloride, such as an acrylic copolymer, a vinyl chloride-urethane copolymer, and a plasticizer, etc., which imparts flexibility to the copolymer. Examples of plasticizers include phthalate esters such as dioctyl phthalate, fatty acid esters such as aliphatic dibasic acid esters such as dioctyl adipate and dibutyl sebaciate, polyester plasticizers, epoxidized soybean oil, and epoxidized linseed oil. etc. are used. As mentioned above, many plasticizers can be used, but if a large amount of any of them is added, the adhesion to silicone rubber tends to weaken. Among these, there are phthalic acid esters, mainly dioctyl phthalate, and epoxidized soybean oil or epoxidized linseed oil, which can maintain relatively adhesive strength, and these are particularly preferred as plasticizers to be used. Furthermore, non-liquid polymers that give flexibility to vinyl chloride resin, such as urethane,
Additions such as EVA also fall into this category. Further, as stabilizers that impart heat resistance and thermal stability, in addition to metal soaps such as calcium stearate, zinc stearate, magnesium stearate, and lead stearate, organic metal stabilizers and inorganic metal stabilizers of the above metals, Ester stabilizers such as organotin stabilizers, organosilicone stabilizers, and butyl stearate can be used, but preferably metal soaps such as calcium stearate, zinc stearate, lead stearate, barium stearate, and the above Organometallic stabilizers and inorganic metal stabilizers of metals are preferred. The addition polymerization type silicone rubber in the present invention refers to a vinyl group-containing polysiloxane represented by the general formula (1), an organohydrogen polysiloxane represented by the general formula (2), and silica as a reinforcing material. It is a composition that can be solidified into an elastic body by addition polymerizing an inorganic composition with a platinum-based catalyst, and the organohydrogensiloxane unit represented by the general formula (2) is formed by the general formula (1). An organohydrogenpolysiloxane having two or more hydrogen atoms in one molecule is contained in an amount sufficient to provide hydrogen atoms directly bonded to silicon atoms at a ratio of 1 to 6 times the total vinyl groups shown in It is something that exists. [In the formula, R ₁ to _{R 5} , R ₇ to _{R 10} : Same or different monovalent hydrocarbon groups having 6 or less carbon atoms R ₆ : Hydrogen group or same or different monovalent hydrocarbon groups having 3 or less carbon atoms Group m: Positive integer n: Integer from 2 to 100 l: Positive integer from 0 to 100] The ethylene-vinyl alcohol copolymer in the present invention is usually prepared by saponifying the ethylene-vinyl acetate copolymer. It is preferable to use a resin obtained by using a resin having a particularly high oxygen gas barrier property. It is generally known that the oxygen gas barrier properties of ethylene-vinyl alcohol copolymers deteriorate when they absorb moisture. This is based on the discovery that, surprisingly, the barrier properties against plasticizers such as or,
When adhering a pre-formed ethylene-vinyl alcohol copolymer and a soft vinyl chloride resin via an addition-polymerized liquid silicone rubber, the ethylene-vinyl alcohol copolymer may be used as is, but In order to bond the pre-cured addition polymer silicone rubber and the ethylene-vinyl alcohol copolymer, the ethylene-vinyl alcohol copolymer must contain at least 30 mol of organohydrogensiloxane units per 100 parts by weight of the resin. % or more of organohydrogenpolysiloxane in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight. If the amount of organohydrogenpolysiloxane added is less than 0.01 parts by weight, there will be no effect and adhesion will be difficult, and if it exceeds 5 parts by weight, transparency will be markedly reduced and the ethylene-vinyl alcohol copolymer will become a barrier to plasticizers. Sexuality decreases. There are two methods for producing the flexible vinyl chloride resin multilayer laminate in the present invention. The first method is to prepare a pre-formed soft vinyl chloride resin molded product (for example, a sheet) and a pre-formed ethylene-vinyl alcohol copolymer molded product (for example, a film), and then Addition-polymerizable liquid silicone rubber or its organic solvent solution is applied to the molded product by a coating method, a spray method, etc., and the other molded product is laminated on top of the molded product without introducing air, and then heated in a heating furnace. 40℃ to 130℃ depending on the temperature, preferably 80℃
At a temperature of 5 minutes to 10 hours, preferably 10 to 120°C.
The layers are laminated and integrated over a period of minutes to 3 hours. Alternatively, a cured layer of addition polymerizable silicone rubber may be further provided on the surface of the ethylene-vinyl alcohol copolymer by a similar method. The second manufacturing method consists of a pre-molded soft vinyl chloride resin molded article (e.g. tube), an organic solvent solution of addition polymerized liquid silicone rubber, and an ethylene-vinyl alcohol copolymer to which organohydrogen polysiloxane is added. Prepare each organic solvent solution, apply it to the surface and heat it to 40℃
After heating at 130°C for 5 minutes to 10 hours, and after curing, apply it thereon and dry under reduced pressure at 40°C to 100°C, or further apply on the surface of the ethylene-vinyl alcohol copolymer layer, 40℃～130℃
You can heat it for 5 minutes to 10 hours. The solvent used for the preparation of and is n-hexane, water and n-hexane.
- A mixed solvent of propyl alcohol can be used. Further, the coating method used is a dipping method, a spraying method, etc., but is not particularly limited. Since the multilayer laminate of the present invention is mainly intended for use in the medical field, the outermost layer, which comes into contact with infusions, body fluids such as blood, and living tissues, is an addition polymerization type with excellent antithrombotic properties. Either silicone rubber or ethylene-vinyl alcohol copolymer may be used, but if ethylene-vinyl alcohol copolymer is the outermost layer, it may easily cause cracks or absorb water depending on the application. Since it is easy to use, it is preferable to use addition polymerization type silicone rubber as the outermost layer in applications requiring elasticity. Therefore, when only one side is in contact with biological fluid or tissue, such as sheet-like multilayer laminates used for infusion bags, blood bags, etc., or tube-shaped multilayer laminates used for blood circuits, soft It is sufficient to laminate a soft vinyl chloride resin/addition polymer silicone rubber/ethylene-vinyl alcohol copolymer in this order on only one side of the vinyl chloride resin, and then laminate another layer of addition polymer silicone rubber if necessary. For applications that are inserted or indwelled into the body, such as catheters, and both sides are in contact with biological fluids or tissues, soft vinyl chloride resin/addition polymer silicone rubber/ Layering ethylene-vinyl alcohol copolymer in this order,
Addition polymerization type silicone rubber is further laminated as necessary. The thickness of each layer in the soft vinyl chloride resin multilayer laminate of the present invention is not particularly limited, but in view of strength, transparency, flexibility, price, etc., the soft vinyl chloride resin layer accounts for most of the thickness. The thickness of the ethylene-vinyl alcohol copolymer layer is desirably 1 μ to 50 μ, preferably 5 μ to 10 μ in order to provide a barrier effect against the plasticizer. Furthermore, the thickness of the addition-polymerized silicone rubber layer is to play a role in adhesion to the ethylene-vinyl alcohol copolymer or soft vinyl chloride resin, and to impart rubber-like elasticity to the multilayer laminate. 10μ to 200μ, preferably 30μ to 100μ
is suitable. The mechanism of adhesion between each layer of the multilayer laminate according to the present invention has basically already been disclosed in Japanese Patent Application No. 58-95689 and Tokugan No. 58-203699, but based on these findings, The adhesion mechanism between the soft vinyl chloride resin and the addition polymerization type liquid silicone rubber, and between the ethylene-vinyl alcohol copolymer and the addition polymerization type liquid silicone rubber is as shown in equation (3), respectively. It is presumed that the organohydrogensiloxy group contained in the organohydrogenpolysiloxane in the liquid silicone rubber undergoes an addition reaction with the unsaturated double bond in the soft vinyl chloride resin or ethylene-vinyl alcohol copolymer. (〓) Soft vinyl chloride resin or ethylene-
Unsaturated double bond in vinyl alcohol copolymer [Effect of the invention] The soft vinyl chloride resin multilayer laminate thus obtained has
Without compromising toughness, flexibility, or transparency, there is almost no elution of plasticizers, which was a drawback in the past, and the outermost layer has excellent antithrombotic properties, making it an ideal solution for infusions, especially in the medical field. It can be widely used in blood circuits, catheters, etc., and is extremely useful. The effects of the present invention will be explained below with reference to Examples. Example 1 Vinyl chloride resin (SX-DH manufactured by Sumitomo Chemical Co., Ltd.)
To 100 parts by weight, 40 parts by weight of dioctyl phthalate, 0.03 parts by weight of each of a calcium-based stabilizer and a zinc-based stabilizer in terms of metal weight, and 10 parts by weight of epoxidized soybean oil were added, and rolled at 190°C for 7 minutes. The mixture was kneaded and then press-molded at 200°C for 3 minutes to obtain a sheet with a thickness of 1 m/m. On the other hand, ethylene
A vinyl alcohol copolymer (EVAL F manufactured by Kurera Co., Ltd.) was molded using a 30 m/mφ extruder to obtain a film with a thickness of 50 μm. The above soft vinyl chloride resin sheet was cut into 10 cm square pieces, and the viscosity at 25°C was shown on the surface.
18000CS, and 10 mol% of trimethylsiloxane units are added to 100 parts by weight of dimethylpolysiloxane, which has dimethylvinylsilyl groups at both ends of the molecular chain.
Polysiloxane 5 consisting of 40 mol% dimethylsiloxane units and 50 mol% methylhydrogen siloxane units
Part by weight, 20 parts by weight of silica, and 0.2 parts by weight of an isopropyl alcohol solution of chloroplatinic acid (platinum content: 1%) were added to add an addition polymerization type liquid silicone rubber to a thickness of 50μ using a spacer for coating. Then, the above Eval film (cut into 10 cm squares) was placed on top of it (this is referred to as multilayer laminate A), and the above addition-polymerizable liquid silicone rubber was placed on top of the Eval film. Each layer coated with a thickness of 50 μm (this will be referred to as multilayer laminate B) was placed in an oven and heated at 100°C for 90 minutes to form two types of soft vinyl chloride resin multilayer laminates A and B. Obtained. Each of these multilayer laminates was strongly adhesively integrated. These multilayer laminates and the above-mentioned soft vinyl chloride resin sheet (comparative example) were each cut to a size of 7 cmφ, and the soft chloride resin sheet of evaluation sheet 4 was placed on the back of the lid 2 of a metal container as shown in Figure 1. Set the container body 1 so that the vinyl resin layer is on the lid side.
(Capacity: 500ml) Pour 100ml of distilled water and cover with a lid.
The material was vibrated in the direction of arrow A for a certain period of time at 3 Hz in a constant temperature bath at 40° C. to extract the plasticizer, etc. Thereafter, each extract was taken out, and the amount of dioctyl phthalate in the solution was measured by gas chromatography. The results were as shown in Table 1.

[Table] Furthermore, in order to examine the antithrombotic properties of the outermost surface of these multilayer laminates and the surface of the soft vinyl chloride resin sheet (comparative example), each sheet was cut into 5 m/m square pieces, and each sheet was cut with the evaluation side facing up. Attach it to the bottom of a 50m/mφ glass flat tray with double-sided adhesive tape, and pour 5ml of fresh dog blood from above.
After incubating at ℃ for 4 minutes, blood was gently washed away with distilled water, treated with 1% glutaraldehyde aqueous solution for 2 hours, further washed with distilled water, air-dried, and the surface of each specimen was subjected to scanning electron microscopy. Observed at. The results are shown in Table 2.

[Table] As described above, the flexible vinyl chloride resin multilayer laminate of the present invention not only exhibits extremely low elution of plasticizers but also extremely low platelet adhesion, making it a particularly useful material in the medical field. I understand that. Example 2 50 parts by weight of dioctyl phthalate per 100 parts by weight of vinyl chloride resin (700-D manufactured by Toyosotatsu Co., Ltd.)
A molding compound was prepared by adding 0.03 parts by weight of each of a calcium-based stabilizer and a zinc-based stabilizer in terms of metal weight, and 5 parts by weight of epoxidized soybean oil. , outer diameter
A tube of 7m/m was created. This tube was cut into a length of approximately 2 m. On the other hand, for 100 parts by weight of dimethylpolysiloxane, which has a viscosity of 16000 cs at 25°C and has dimethylvinylsilyl groups at both ends of the molecular chain, 12 mol% of trimethylsiloxane units, 40 mol% of dimethylsiloxane units, and methylhydrogen siloxane units
35% by weight of an addition polymerization type liquid silicone rubber prepared by adding 7 parts by weight of polysiloxane consisting of 48 mol%, 25 parts by weight of silica, and 0.3 parts by weight of an isopropyl alcohol solution of chloroplatinic acid (platinum content: 5%).
Prepare an n-hexane solution, connect the approximately 2m tube mentioned above to a suction pump, and gently suction it. When the suction reaches almost the entire inner surface of the tube, remove it from the suction pump, leave the tube vertically, and remove it from the tube. After air-drying the solution until it no longer dripped, it was heated in a vertical dryer at 110° C. for 90 minutes. After that, the tube was taken out and ethylene-vinyl alcohol copolymer (EVAL E manufactured by Kuraray Co., Ltd.) was added.
was dissolved in a solvent of distilled water: isopropyl alcohol: n-propyl alcohol = 1:1:1.
A weight percent solution was prepared, and the inner surface of the tube was coated in the same manner as described above, followed by drying at 70° C. for 3 hours in a vertical vacuum dryer. The thus obtained multilayer laminated tube and the uncoated soft vinyl chloride resin tube (comparative example) were each connected to a blood pump, and physiological saline (48°C, 300 ml) was added at a rate of 100 ml/min. After circulating for 5 hours to extract the plasticizer, etc.
Each extract was analyzed by gas chromatography, and the amount of eluted dioctyl phthalate was determined. The results are shown in Table 3, showing that almost no dioctyl phthalate was eluted from the multilayer laminated tube of the present invention.

【table】 [Brief explanation of drawings]

FIG. 1 is a diagram showing a container used in the elution test of dioctyl phthalate.

Claims (1)

[Scope of Claims] 1. A flexible vinyl chloride resin multilayer laminate, comprising at least three layers of a flexible vinyl chloride resin, an ethylene-vinyl alcohol copolymer, and an addition-polymerized silicone rubber. 2 At least three layers constituting the laminate are soft vinyl chloride resin/addition polymerization silicone rubber/ethylene-vinyl alcohol copolymer, or soft vinyl chloride resin/addition polymerization silicone rubber/
The flexible vinyl chloride resin multilayer laminate according to claim 1, characterized in that ethylene-vinyl alcohol copolymer/addition polymerization type silicone rubber are laminated in this order. 3. Claim 1 or 2, wherein the metal in the stabilizer added to the soft vinyl chloride resin is one or more of calcium, zinc, barium, magnesium, and aluminum. 2. The soft vinyl chloride resin multilayer laminate according to item 2. 4. Organohydrogen containing two or more hydrogen atoms in one molecule of the addition-polymerizable silicone rubber in an amount sufficient to provide 1 to 6 hydrogen atoms directly bonded to silicon atoms per vinyl group in the composition. The soft vinyl chloride resin multilayer laminate according to claim 1 or 2, characterized in that it contains polysiloxane. 5. A patent characterized in that the ethylene-vinyl alcohol copolymer contains 0.01 to 5 parts by weight of organohydrogenpolysiloxane having at least 30 mol% of organohydrogensiloxane units based on 100 parts by weight of the resin. Claim 1 or 2
The soft vinyl chloride resin multilayer laminate described in Section 3. 6 Apply addition polymerization type liquid silicone rubber to the surface of a pre-formed soft vinyl chloride resin molded product, and contact the surface with a pre-formed ethylene-vinyl alcohol copolymer molded product, or further apply the ethylene-vinyl alcohol copolymer molded product to the surface. A method for producing a flexible vinyl chloride resin multilayer laminate, which comprises applying an addition-polymerizable liquid silicone rubber to the surface of a vinyl alcohol copolymer and heating it at 40°C to 130°C for 5 minutes to 10 hours. 7. Prepare a pre-formed soft vinyl chloride resin molded article, an organic solvent solution of addition polymerized liquid silicone rubber, and an organic solvent solution of ethylene-vinyl alcohol copolymer added with organohydrogen polysiloxane, and Apply
After curing by heating at 40°C to 130°C for 5 minutes to 10 hours, coat the layer and dry under reduced pressure at 40°C to 100°C, or further coat the surface of the ethylene-vinyl alcohol copolymer layer. A method for producing a soft vinyl chloride resin multilayer laminate, which comprises coating and heating at 40°C to 130°C for 5 minutes to 10 hours.